Triacetoxyperiodinane → Ammonium Hydroxide

HRID 1677430Notes

Reaction equation

HRID 1677430 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]([CH:15]([OH:47])[C:16]2[C:24]3[C:19](=[N:20][CH:21]=[C:22]([C:25]4[CH:30]=[C:29]([O:31][CH3:32])[C:28]([O:33][CH3:34])=[C:27]([O:35][CH3:36])[CH:26]=4)[N:23]=3)[N:18]([Si:37]([CH:44]([CH3:46])[CH3:45])([CH:41]([CH3:43])[CH3:42])[CH:38]([CH3:40])[CH3:39])[CH:17]=2)([CH3:14])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)Cl>[NH4+:8].[OH-:5].[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]([CH3:14])([C:15]([C:16]2[C:24]3[C:19](=[N:20][CH:21]=[C:22]([C:25]4[CH:26]=[C:27]([O:35][CH3:36])[C:28]([O:33][CH3:34])=[C:29]([O:31][CH3:32])[CH:30]=4)[N:23]=3)[NH:18][CH:17]=2)=[O:47])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]([CH3:14])([C:15]([C:16]2[C:24]3[C:19](=[N:20][CH:21]=[C:22]([C:25]4[CH:26]=[C:27]([O:35][CH3:36])[C:28]([O:33][CH3:34])=[C:29]([O:31][CH3:32])[CH:30]=4)[N:23]=3)[N:18]([Si:37]([CH:38]([CH3:40])[CH3:39])([CH:41]([CH3:43])[CH3:42])[CH:44]([CH3:45])[CH3:46])[CH:17]=2)=[O:47])[CH2:10][CH2:9]1)=[O:7])([CH3:3])([CH3:4])[CH3:2]

Participants

6

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 595406034-{hydroxy-[5-triisopropylsilanyl-2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazin-7-yl]-methyl}-4-methyl-piperidine-1-carboxylic acid tert-butyl ester

Product 3

HCID 14923Ammonium HydroxideHCID 595405814-methyl-4-[5-triisopropylsilanyl-2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazine-7-carbonyl]-piperidine-1-carboxylic acid tert-butyl esterHCID 595408684-methyl-4-[2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazine-7-carbonyl]-piperidine-1-carboxylic acid tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 4-{hydroxy-[5-triisopropylsilanyl-2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazin-7-yl]-methyl}-4-methyl-piperidine-1-carboxylic acid tert-butyl ester from above (950 mg, ˜1.4 mmol) in CH2Cl2 (5 mL) was added Dess-Martin periodinane (900 mg, 2.1 mmol) portionwise. The resultant orange suspension was allowed to stir for 1 h and partitioned between 1:1 saturated Na2S2O3:saturated NaHCO3 and CH2Cl2. The aqueous phase was extracted with CH2Cl2 and the combined organic phases were dried over Na2SO4 and concentrated to give a tan solid. The crude product was purified by flash chromatography using 25 g of silica gel and 0-30% of 9.5:0.5 MeOH:conc NH4OH in CH2Cl2 as eluant to afford 150 mg of impure 4-methyl-4-[2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazine-7-carbonyl]-piperidine-1-carboxylic acid tert-butyl ester, M+Na 533, and 0.24 g of impure 4-methyl-4-[5-triisopropylsilanyl-2-(3,4,5-trimethoxy-phenyl)-5H-pyrrolo[2,3-b]pyrazine-7-carbonyl]-piperidine-1-carboxylic acid tert-butyl ester, M+Na 689.

Workup

  1. custompartitioned between 1:1 saturated Na2S2O3
  2. extractionThe aqueous phase was extracted with CH2Cl2
  3. dry with materialthe combined organic phases were dried over Na2SO4
  4. concentrationconcentrated
  5. customto give a tan solid
  6. customThe crude product was purified by flash chromatography

Sources & evidence

ORD record
ord-2693fa902f554476aed363d3a008d3ae
Source dataset
uspto-grants-2011_08
Patent number
US08008298B2

Reaction notes

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